Strain-Work Function Relationship in Single-Crystal Tetracene

Understanding the impact of strain on organic semiconductors is important for the development of electronic devices and sensors that are subject to environmental changes and mechanical stimuli; it is also important for understanding the fundamental mechanisms of charge trapping. Following our previous study on the strain effects in rubrene, we present here only the second example of the strain-work function relationship in an organic semiconductor; in this case, the benchmark material tetracene. Thin, platelike single crystals of tetracene with large (001) facets were laminated onto silicon and rubber substrates having significantly different coefficients of thermal expansion; mechanical strain in tetracene was subsequently induced by varying the temperature of the assembly. Tensile and compressive strains parallel to the (001) major facet were measured by grazing incidence X-ray diffraction, and the corresponding shifts in the electronic work functions were recorded via scanning Kelvin probe microscopy (SKPM). The work function of the tetracene (001) crystal surface directly correlated with the net mechanical strain and increased by ∼100 meV for in-plane tensile strains of 0.1% and decreased by approximately the same amount for in-plane compressive strains of -0.1%. This work provides evidence of the general and important impact of strain on the electrical properties of van der Waals bonded crystalline organic semiconductors and thereby supports the hypothesis that heterogeneous strains, for example in thin films, can be a major source of static electronic disorder.